固态后缩聚方法合成高分子量的含磷热致性液晶共聚酯

为了获得较高分子量的具有高阻燃性的热致性液晶高分子,通过固态聚合方法合成了一种基于对羟基苯甲酸、对苯二甲酸、乙二醇和含磷菲环取代二酚的高热稳定性、较低相转变温度和宽的液晶相转变温度范围的含磷液晶共聚酯(BDQTEP),并对该含磷液晶共聚酯预聚物(pre-BDQTE)在不同固态聚合条件下获得的聚合物热性能和液晶性进行了研究.对其固态反应速率控制进行了初步的探讨,当反应温度为235℃时,固态聚合反应较为理想.在聚合的初始阶段,共聚酯特性黏数[η]、黏流温度Tf和羧基浓度[COOH]均随聚合时间而明显变化,但在6 h后变化较小,几乎不变.通过固态后缩聚,将熔融聚合获得的特性黏数[η]=0.44 dL/g的含磷液晶共聚酯BDQTE的特性黏数提高了近两倍.     

热致液晶性聚合物——含萘环主成分为对羟基苯甲酸的全芳香族共聚酯

由对乙酰氧基苯甲酸、对苯二酚二乙酯、2,6-萘二甲酸及间苯二甲酸四种单体通过熔融缩聚反应,合成了全芳香族四组分共聚酯。在一定的组成范围内,共聚酯熔体有很好的液晶性。本文重点讨论了聚合物的组成与性质的关系,热谱特征和液晶相行为。     

热致液晶共聚酯与聚酯热塑弹性体复合物的制备与性能

原位缩聚法制备了一系列(对羟基苯甲酸-对苯二甲酸-间苯二酚)(HB-TA-RES)热致液晶共聚酯与聚对苯二甲酸丁二酯-聚四亚甲基醚热塑弹性体(PBT-PTMG)复合物,并用POM,TGA,WAXD,SEM及动态应力流变仪等手段进行了表征.复合物在较宽的共聚酯含量范围(30 wt%~70 wt%)或共聚酯组成不同时(共聚酯中HB含量20 mol%~80 mol%)均具有热致液晶行为.当复合物中共聚酯含量≤50 wt%以及共聚酯中对羟基苯甲酸(HB)含量≤60 mol%时,共聚酯分子的结构更加均匀化,结晶组分的结晶行为受到限制,基体与液晶组分具有较好的复合效果,不表现明显的相分离行为.复合物与相应的纯共聚酯相比,具有较好的热稳定性;其粘度均比基体PBT-PTMG小.当复合物中共聚酯含量≥30 wt%时,其粘度下降尤为显著,表明其具有较好的加工性.     

热致性共聚酯液晶的研究——以双酚-对苯二甲酸酯为间隔段

热致性共聚酯液晶由于具有优异的热、机械及加工等性能,引起人们对其应用及基础研究的重视。本实验室曾对以不同长度碳链为软间隔段的共聚酯进行了研究,在产物介晶单元含量不高(约20％)时即可表现出明显液晶性。本文选用以双酚A(BPA)或双酚S(BPS)-对苯二甲酸酯为间隔段进行了研究。     

序列结构对液晶共聚酯性能的影响

本文通过熔融酯交换和Schottern-Baumann缩聚反应合成了两类组成相同而序列结构不同的基于对羟基苯甲酸、对苯二甲酸和二元酚的三元共聚酯,用热台偏光显微镜、DSC和X-射线衍射,较详细地研究了序列结构对液晶相类型、转变温度和固态结构等的影响。结果表明,无规共聚酯较规则共聚酯的熔化温度普遍降低;但序列结构的差异并不改变液晶相类型,规则共聚酯和无规共聚酯均为热致向列型液晶,两类共聚酯固态结构的差异可用结构单元的相似性进行解释。     

含X-型和棒型两种液晶基元的主链型共聚酯

采用高温溶液缩聚方法,合成了一系列不同配比的含X-型和棒型两种液晶基元的主链型芳族共聚酯。经检测,所有样品均具有热致液晶性。本文对这类共聚酯的液晶行为进行了研究。     

一类可纺丝的全芳香热致性液晶共聚酯的合成和表征

利用Higashi芳香聚酯直接缩聚法的原理 ,采用一步混合投料直接缩聚的方法 ,以对羟基苯甲酸(PHB)、间苯二甲酸 (MPA)、4 ,4′ 二羟基二苯酮 (DHBP)和对苯二酚 (HQ)为单体原料 ,合成了全芳香共聚酯 .该合成方法反应条件温和 ,简单易控 ,产物分子量高 .用差热分析 (DSC)、热重分析 (TA)、偏光显微镜 (PLM)、广角X 射线衍射 (WAXD)等测试分析手段对共聚酯的热性能和液晶特性进行了表征 .研究结果表明 ,利用此方法合成所得的聚合物呈明显的向列型热致液晶特性 ,热稳定性高 ,并具有极易成纤的特点 ,有望成为一种可用于纺丝的全芳香热致液晶共聚酯材料     

1,8-辛二酸改性热致液晶共聚酯的制备及其性能

以对羟基苯甲酸、对苯二甲酸和对苯二酚为共聚单体，经乙酰化和熔融缩聚两步法合成三元热致液晶共聚酯。引入长链脂肪族化合物1,8-辛二酸作为改性单体，按不同比例代替对苯二甲酸，制备了一系列含柔性链段的新型四元热致液晶共聚酯。通过傅里叶红外光谱(FT-IR)和核磁共振碳谱(¹³C-NMR)对共聚酯结构进行表征，采用差示扫描量热(DSC)和热失重分析(TGA)表征其热性能，采用偏光显微镜(POM)和X射线衍射(XRD)分析其液晶性能。研究表明，三元液晶共聚酯熔点达407℃，热稳定性优异。随着1,8-辛二酸含量增加，四元共聚酯熔点显著降至214℃，热稳定性较好，最大热分解温度达到428℃。该系列共聚酯显示了典型的向列型液晶织态结构。1,8-辛二酸的引入显著改善了液晶共聚酯的可加工性。     

热致液晶共聚酯对聚丙烯结晶的诱导作用

用差示扫描量热法和光学解偏振法研究了热致液晶性芳香共聚酯与聚丙烯共混物的等温和非多温结晶行为.结果表明,这一热致液晶聚合物对聚丙烯结晶有诱导成核和加速作用.当共聚酯含量在2-5％之间时,聚丙烯的结晶速率最快.偏光显微镜的观察揭示出在聚丙烯熔体中原位形成的液晶聚合物微纤诱导了聚丙烯横穿晶的形成.     

含柔性间隔基的热致液晶性共聚酯的合成

将己二酸、辛二酸、癸二酸、1,10-十二烷基羧酸经酰氯化后,分别与对羟基苯甲酸合成,得到了四种二元羧酸以及与其相应的四种二元酰氯,并发现前者具有热致液晶性。 将上述单体与对苯二酚、氯代对苯二酚以及联苯二酚用溶液缩聚的方法合成了十二种规则共聚酯,并用热台偏光显微镜、DSC、X-衍射等方法对共聚酯进行了表征。结果发现各共聚酯均为向列型热致液晶,并都具有较宽的液晶态温度范围。通过改变分子结构可使共聚酯的熔点在150—300℃之间变化。     

结晶度对微波作用下PET水解解聚的影响

本文对微波作用下PET的中性水解解聚反应中原料结晶度的影响进行了研究.     

动态硫化EPDM／PP共混体系中PP相的结晶度及晶体结构的研究

研究了动态硫化ＥＰＤＭ／ＰＰ共混物中ＰＰ相的结晶度及晶体结构,同时讨论了制备工艺条件以共混物中ＰＰ相的结晶度和晶体结构的影响。结果表明：在动态硫化ＥＰＤＭ／ＰＰ共混物中,硫化的ＥＰＤＭ的分子键没有穿入ＰＰ的晶区,ＰＰ的结晶度随ＥＰＤＭ含量的增加而下降。提高共混温度,加入软化剂或碳黑均使共混物中ＰＰ的结晶度降低,共混时间１５ｍｉｎ时,共混物中ＰＰ相的结晶度最低,但ＰＰ的晶格不受制备工艺条件的影响。     

Crystallinity changes in plastically deformed isotactic polypropylene evaluated by x‐ray diffraction and differential scanning calorimetry methods

The crystallinity of isotactic polypropylene (iPP), when deformed with plastic plane‐strain compression, was studied with wide‐angle X‐ray scattering (WAXS) and differential scanning calorimetry (DSC) techniques. A comparison of the obtained crystallinity data with annealed iPP samples was performed. The material used in this study was commercial iPP (weight‐average molecular weight = 117.400 g/mol; number‐average molecular weight = 17.300 g/mol). A significant decrease in the crystallinity was observed with increasing deformation pressure when the X‐ray method was employed, whereas only a small decrease was registered when the DSC method of crystallinity determination was used. However, the annealed iPP samples demonstrated a slight crystallinity increase when evaluated by both techniques. The reason for the difference between WAXS and DSC crystallinity results is discussed. This study of iPP specimens subjected to large deformation led us to the conclusion that the WAXS method provides accurate crystallinity values for the deformed material, whereas the values obtained by the DSC method do not reproduce the real crystallinity of the deformed material. This is due to the inherent heating process of the method, which causes a relaxation process and a significant change in the crystallinity of the deformed material, providing values nearer to its intrinsic equilibrium state. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 896–903, 2002     

蒸压硅酸盐制品水化产物的结晶度分析

利用烧失量和酸溶法测定不同固体废物蒸压样品的结合水量和溶出差,研究固体废物蒸压样品中水化产物量、结晶度与其强度的关系。结果表明,粉煤灰、废玻璃、废混凝土蒸压样品的结晶度较低,钢渣蒸压样品的结晶度较高。蒸压样品的溶出差、结合水量和结晶度与水化产物种类有关。蒸压样品的结晶度可间接表达结晶良好的水化产物占总水化产物量的多少,并可用来确定不同蒸压制品的合理养护制度,指导蒸压制品的工艺优化。蒸压样品的结晶度存在合理范围。     

Effect of γ-dose rate on crystallinity and morphological changes of γ-sterilized biomedical polypropylene

The present work is aimed to study the changes in crystallinity and morphology of biomedical polyolefins after γ-sterilization. The isotactic polypropylene (iPP) films were sterilized by γ-radiation and the changes were characterized by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and atomic force microscopy (AFM) techniques. The effect of dose rate on crystallinity changes also was focused. It was found that crystallinity and morphology significantly changed with γ-irradiation. There was an increase in crystallinity up to 10 kGy accompanied with decrease in viscosity and mechanical properties. The changes in crystallinity mainly depend on γ-irradiation dose and dose rate. The rise in crystallinity was attributed to chain scission and forming new perfect lamellae. However, the reduction was accompanied by occurrence of γ- and β-phases and crosslinking. Possible explanations for transitions in phases are also discussed based on our results.     

煤焦的晶格结构,本征反应活性和密度初探

通过对低变质程度烟煤的镜质组分分别在空气和高纯氧中所得中温焦炭的密度和晶格化程度的初步研究，并作了链条锅炉飞灰炭的本征反应活性和密度关系比较，认为煤在不同气氛中加热其晶各化结构增强的决定性作用是温度，其次是煤在加热中的停留时间，煤焦的密度大小可作为煤焦晶格化程度的一种表征，煤焦的本征反应活性与煤焦密度和晶格化程度具有相关性。     

Influence of crystal polymorphism on crystallinity calculation of poly(l-lactic acid) by infrared spectroscopy

Vibrational spectroscopic methods have been used to determine the crystallinity of poly(l-lactic acid) (PLLA), which is the most popular bio-plastic today. However, it is found that influence of crystal polymorphism of PLLA on the quantitative method proposed for crystallinity calculation based on IR technique has seldom been considered. Herein, by preparing a set of PLLA specimens with different crystallinity and crystal forms, the absorption coefficient ratios between amorphous and crystal bands for evaluating the absolute crystallinity of PLLA α and α′ crystal form have been derived, respectively. In addition, a comparison of the proposed IR method with other techniques used to analyze crystallinity of PLLA such as X-ray diffraction (XRD) and differential scanning calorimetry (DSC) is presented. The origin of the disagreement on the results of quantitative measurements of crystallinity by different methods is also discussed. This study provides a simple spectral method to determine the crystallinity of PLLA with various crystal modifications.     

An attenuation total reflectance fourier transform spectroscopic study of crystallinity in the bulk and on the surface of aqueous and aqueous salt cryogels of poly(vinyl alcohol)

The crystallinity of poly(vinyl alcohol) in the bulk and on the surface of cryogels of this polymer prepared in the form of thick disks from solutions in pure water and in water containing potassium chloride is studied via attenuation total reflectance FTIR spectroscopy. The crystallinity values of the upper and lower surfaces of the samples are found from the attenuation total reflectance IR spectra of these surfaces. To determine the crystallinity in the bulk, a sample is cut in half in the middle of its thickness to measure the spectrum of the cut surface. It is found that, in the bulk of a salt-free cryogel, the content of the crystalline phase of the polymer is significantly higher (by a factor of 1.5) than that on the surface. Addition of a salt increases the degree of crystallinity in the bulk and does not change the crystallinity of the surface. Cryogelation mechanisms explaining the increased crystallinity in the bulk of the cryogel and the crystallizing effect of the salt additive are proposed.     

The influence of crystallinity distribution on small-angle x-ray scattering from semicrystalline polymers

Theoretical x-ray scattering curves have been developed for the lamellar structure in semicrystalline polymers in which there are present distributions of lamellar thickness and crystallinity. The models have been tested against samples of linear low-density, low-density and crosslinked polyethylenes. When variation in crystallinity is present in a material, a major effect is an increase in the magnitude of near-zero angle scattering. The Bragg maximum can appear as an ill-defined hump on an apparently high level of background scattering. The shape of the Bragg peak is influenced more by crystallinity distribution than by lamellar thickness distribution. Of the polymers we have studied so far only linear low density polyethylene shows significant crystallinity distribution effects. A “rule-of-thumb” method for rapid estimation of crystallinity distribution effects has been developed, obviating the need for lengthy simulation.     

Contribution of the secondary crystallization to the overall crystallinity of heatset polyester

The crystallinity of poly(ethyleneterephthalate) has been determined by differential scanning calorimetry and by density. The results obtained by calorimetry show that the increment in the crystallinity due to the heatsetting treatment is produced by the increase of the crystallinity corresponding to the premelting endothermic peak.